US5003084A - Process for preparing alkylene carbonates - Google Patents

Process for preparing alkylene carbonates Download PDF

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Publication number
US5003084A
US5003084A US07/481,929 US48192990A US5003084A US 5003084 A US5003084 A US 5003084A US 48192990 A US48192990 A US 48192990A US 5003084 A US5003084 A US 5003084A
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United States
Prior art keywords
alkylene
glycol
alkyl group
alkylene glycol
carbon atoms
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Expired - Fee Related
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US07/481,929
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English (en)
Inventor
Wei-Yang Su
George P. Speranza
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Huntsman Corp
Huntsman Petrochemical LLC
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Texaco Chemical Co
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Priority to CA002032221A priority patent/CA2032221A1/en
Priority to EP91301078A priority patent/EP0443758A1/de
Priority to JP03045646A priority patent/JP3085722B2/ja
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Assigned to UNITED STATES TRUST COMPANY OF NEW YORK (AS COLLATERAL AGENT) reassignment UNITED STATES TRUST COMPANY OF NEW YORK (AS COLLATERAL AGENT) SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HUNTSMAN CORPORATION (FORMERLY TEXACO CHEMICAL COMPANY)
Assigned to TEXACO INC. reassignment TEXACO INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HUNTSMAN CORPORATION ( FORMERLY TEXACO CHEMICAL COMPANY )
Assigned to HUNTSMAN CORPORATION reassignment HUNTSMAN CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). Assignors: TEXACO CHEMICAL COMPANY
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Assigned to HUNTSMAN PETROCHEMCIAL CORPORATION reassignment HUNTSMAN PETROCHEMCIAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HUNSTMAN CORPORATION
Assigned to BANKERS TRUST COMPANY reassignment BANKERS TRUST COMPANY SECURITY AGREEMENT Assignors: HUNTSMAN PETROCHEMICAL CORPORATION
Assigned to HUNTSMAN CORPORATION reassignment HUNTSMAN CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: UNITED STATES TRUST COMPANY OF NEW YORK
Assigned to BANKERS TRUST COMPANY reassignment BANKERS TRUST COMPANY SECURITY AGREEMENT Assignors: HUNTSMAN PETROCHEMICAL CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates

Definitions

  • the present invention relates to the production of alkylene carbonates.
  • this invention relates to a novel process for the preparation of alkylene carbonates, such as 1,2-butylene carbonate, from the corresponding alkylene glycol and urea.
  • alkylene carbonates such as 1,2-butylene carbonate
  • 1,2-butanediol and urea are reacted in the presence of nitrogen and, optionally, in the presence of a tin catalyst to prepare 1,2-butylene carbonate.
  • the invention is particularly advantageous in its simplicity, use of mild conditions, low cost of starting materials and optional requirement for a catalyst.
  • U.S. Pat. No. 2,773,070 describes one of the earlier methods of preparing alkylene carbonates which comprises reacting an alkylene oxide with a molar excess of carbon dioxide at a temperature between 100° C. and 225° C. and a pressure in excess of 300 psig in the presence of a catalyst comprising one of a specified group of ammonium halides.
  • Venturello and D'Aloisio have described a method of preparing 1,2-alkanediyl carbonates in high yields in short reaction times under mild conditions without the drawbacks of toxic or hazardous reagents or high temperatures or the formation of undesired glycols which are hard to separate from cyclic carbonates.
  • This method comprises stirring the corresponding vic-halohydrins with tetramethyl ammonium hydrogen carbonate in acetonitrile. See "A Convenient Synthesis of 1,2-Alkanediyl Carbonates.” Synthesis (1985), 1, 33.
  • cyclocarbonates are prepared from a vicinal halo-hydrin and alkali bicarbonates by heating in aprotic organic solvents such as dimethyl sulfoxide, acetonitrile and dimethylformamide.
  • This invention concerns a novel process for the production of alkylene carbonates from the reaction of the corresponding alkylene glycol and urea, optionally in the presence of a tin catalyst at atmospheric pressure and a temperature of from about 130° C. to 200° C.
  • the process demonstrates a conversion of glycol as high as 95% and a selectivity for the alkylene carbonate as high as 96%.
  • this process would be very attractive commercially by virtue of its use of less expensive and less hazardous reactants, mild conditions and the efficiency of the process.
  • an alkylene glycol having about 3 to 18 carbon atoms is reacted with urea in the presence of nitrogen to produce an alkylene carbonate.
  • the reaction can be represented by the following equation: ##STR2## where R represents an alkyl group containing 1 to 16 carbons.
  • the alkylene glycol can be selected from the group of alkylene glycols having the following structures: ##STR3## where R is an alkyl group containing 1 to 16 carbon atoms and R' is H or an alkyl group containing 1 to 8 carbons. Suitable alkylene glycols included in this group are cyclohexane diols, aryl-aliphatic 1,2 diols and internal 1,2 glycols.
  • Vicinal glycols having the structure: ##STR4## can be used wherein R and R' are defined as above and suitable examples include 1,2-cyclohexane diol and styrene glycol.
  • the alkylene glycol is represented by the structure: ##STR5## where R is an alkyl group containing 1 to 16 carbon atoms. Preferably the alkylene glycol will contain about 3 to 8 carbon atoms.
  • One group of reactants which are effective are 1,2-diols. Examples of suitable 1,2-diols include 1,2-butanediol, 1,2-propanediol, 1,2-hexanediol, cyclohexane 1,2-diol and 1,2-styrene diol. Good results were observed when R was methyl or ethyl as in the case of 1,2-propanediol or 1,2-butanediol. It is worth noting that greater polarity of the alkylene glycol seems to have an adverse effect on selectivity. The reaction proceeds more efficiently with 1,2-butylene glycol than 1,2-propylene glycol which in turn is preferred over 1,2-ethylene glycol.
  • a solvent is not necessary to carry out the process of the invention, however the reaction can be run in the presence of a polar aprotic solvent.
  • Polar aprotic solvents include acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, diethylformamide and diethylacetamide.
  • the preferred polar aprotic solvents are amides such as dimethyl acetamide and dimethylformamide.
  • tin-containing compounds which may be used as the catalyst include the dialkyl tin dicarboxylates and tin salts of organic carboxylic acids. Good results were observed using the commercially available tin catalyst T-12.
  • T-12 is dibutyl tin dilaurate and is manufactured by M and T Chemicals. Where the catalyst was used the ratio of reactants to catalyst was not critical.
  • Reaction conditions are generally mild, but can vary according to starting materials.
  • the process of the invention is conducted at atmospheric pressure.
  • the process can be adapted so the reaction can be run under pressure as long as some method is available for eliminating the ammonia. Where the reaction is conducted under pressure, however it would be particularly undesirable for the pressure to exceed 500 psig.
  • the process of the invention is conducted at relatively mild temperatures. Generally the temperature range is from about 100° C. to 250° C. The preferred temperature range is from about 130° C. to 200° C. As demonstrated in the examples, good results were observed using temperatures in the range of 170° C.-180° C.
  • the preferred residence time is in the range of 1 to 5 hours.
  • the alkylene glycol/urea ratios may be those required by the stoichiometry of the reaction, but they may also vary within rather wide intervals.
  • the amount of alkylene glycol employed is in the range of 1 to 5 moles of glycol group per 1 to 5 moles of urea. Where a ratio in the range of 2 moles of urea per mole of 1,2-butanediol was used (Example 3) a 95% conversion of 1,2-butanediol and 96% selectivity for 1,2-butylene carbonate was observed.
  • alkylene glycol and urea are introduced into the reaction vessel.
  • the reaction mixture was heated up to the desired temperature and the ammonia was released from the reaction.
  • the desired products of this process according to the invention are alkylene carbonates, especially 1,2-propanediol and 1,2-butanediol.
  • Example 1 The procedure of Example 1 was followed except 1.5 g of T-12 catalyst (Tin catalyst) was also charged. About 110 g of reaction mixture was recovered. GC and NMR analyses showed that 99% selectivity of 1,2-butylene carbonate was obtained with 64% conversion of 1,2-butanediol.
  • Example 1 The procedure of Example 1 was followed except that 120 g of urea was charged. About 137 g of reaction mixture was recovered. GC and NMR analyses showed that a 96% selectivity of 1,2,-butylene carbonate and a 4% selectivity of 5-ethyl-2-oxazolidinone were obtained with 95% conversion of 1,2-butanediol.
  • Example 1 The procedure of Example 1 was followed except that 180 g of 1,2-butanediol was charged. About 206.4 g of reaction mixture was recovered. GC and NMR analyses showed that a 94% selectivity of 1,2-butylene carbonate was obtained with 33% 1,2-butanediol conversion.
  • Example 1 The procedure of Example 1 was followed except that 102 g of 1,2-propanediol was charged. About 123.5 g of reaction mixture was recovered. GC and NMR analyses showed that an 84% selectivity of propylene carbonate was obtained with 43% conversion of 1,2-propanediol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US07/481,929 1990-02-20 1990-02-20 Process for preparing alkylene carbonates Expired - Fee Related US5003084A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US07/481,929 US5003084A (en) 1990-02-20 1990-02-20 Process for preparing alkylene carbonates
CA002032221A CA2032221A1 (en) 1990-02-20 1990-12-13 Process for preparing alkylene carbonates
EP91301078A EP0443758A1 (de) 1990-02-20 1991-02-11 Verfahren zur Herstellung von Alkylenkarbonaten
JP03045646A JP3085722B2 (ja) 1990-02-20 1991-02-20 アルキレンカーボネートの製造法

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US07/481,929 US5003084A (en) 1990-02-20 1990-02-20 Process for preparing alkylene carbonates

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US (1) US5003084A (de)
EP (1) EP0443758A1 (de)
JP (1) JP3085722B2 (de)
CA (1) CA2032221A1 (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091543A (en) * 1990-10-15 1992-02-25 Arco Chemical Technology, Inc. Preparation of cyclic carbonates using alkylammonium and tertiary amine catalysts
US5349077A (en) * 1992-07-31 1994-09-20 Mitsubishi Gas Chemical Company, Inc. Process for producing alkylene carbonates
US5440004A (en) * 1993-05-19 1995-08-08 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for the production of alkylene carbonate
US5489702A (en) * 1993-08-12 1996-02-06 Mitsubishi Gas Chemical Company, Inc. Process for the production of dialkyl carbonate
US5561094A (en) * 1993-12-20 1996-10-01 Saleh; Ramzi Y. Dialkyl isocyanato tin alcoholate catalysts and dimers thereof
WO1998000418A1 (en) * 1996-06-28 1998-01-08 Colgate-Palmolive Company Alkylene carbonates and their preparation
DE102004043990A1 (de) * 2004-09-11 2006-03-30 Lurgi Ag Verfahren zur Herstellung von Kohlensäureestern
US8877948B2 (en) 2008-10-08 2014-11-04 Arkema France Synthesis process of polyol carbonate from polyols, conducted in using a solvent selective for polyols carbonates
WO2014177558A1 (en) * 2013-04-29 2014-11-06 Total Research & Technology Feluy Process for preparing polycarbonates by polymerization of five-membered-ring cyclic carbonates
US20200024227A1 (en) * 2017-04-11 2020-01-23 Sabic Global Technologies B.V. Integrated process for production of glycerol carbonate (4-hydroxymethyl-2-oxo-1, 3-dioxolane) and urea
CN111925351A (zh) * 2020-08-28 2020-11-13 华东理工大学 一种尿素与丙二醇（或乙二醇）连续溶解的方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2778182B1 (fr) * 1998-04-30 2000-07-21 Organisation Nationale Interpr Procede de fabrication de carbonate de glycerol
JP3905242B2 (ja) * 1999-02-24 2007-04-18 花王株式会社 グリセリンカーボネートの製造法
JP4732058B2 (ja) * 2005-08-01 2011-07-27 花王株式会社 グリセリンカーボネートの製造法
FR2916445B1 (fr) * 2007-05-24 2009-07-10 Arkema France Procede de co-production de carbonates cycliques et de nitriles et/ou d'amines gras
GB0903233D0 (en) 2009-02-25 2009-04-08 Univ Cardiff Method for making organic carbonates and sulphur analogues
CN106349207A (zh) * 2016-08-30 2017-01-25 中国科学院山西煤炭化学研究所 一种co2与多元醇间接制备环状有机碳酸酯的工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009183A (en) * 1974-09-30 1977-02-22 Montedison Fibre S.P.A. Process for the preparation of alkylene carbonates
US4344881A (en) * 1981-02-02 1982-08-17 The Dow Chemical Company Process for making alkylene carbonates
US4353831A (en) * 1981-02-02 1982-10-12 The Dow Chemical Company Process for making alkylene carbonates
EP0689705A1 (de) * 1993-03-16 1996-01-03 Reinhard Ender Tragbare kommunikationseinrichtung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07100702B2 (ja) * 1987-07-22 1995-11-01 三井石油化学工業株式会社 環状カ−ボネ−トの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009183A (en) * 1974-09-30 1977-02-22 Montedison Fibre S.P.A. Process for the preparation of alkylene carbonates
US4344881A (en) * 1981-02-02 1982-08-17 The Dow Chemical Company Process for making alkylene carbonates
US4353831A (en) * 1981-02-02 1982-10-12 The Dow Chemical Company Process for making alkylene carbonates
EP0689705A1 (de) * 1993-03-16 1996-01-03 Reinhard Ender Tragbare kommunikationseinrichtung

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091543A (en) * 1990-10-15 1992-02-25 Arco Chemical Technology, Inc. Preparation of cyclic carbonates using alkylammonium and tertiary amine catalysts
US5349077A (en) * 1992-07-31 1994-09-20 Mitsubishi Gas Chemical Company, Inc. Process for producing alkylene carbonates
US5440004A (en) * 1993-05-19 1995-08-08 Mitsubishi Gas Chemical Company, Inc. Method and apparatus for the production of alkylene carbonate
US5489702A (en) * 1993-08-12 1996-02-06 Mitsubishi Gas Chemical Company, Inc. Process for the production of dialkyl carbonate
US5561094A (en) * 1993-12-20 1996-10-01 Saleh; Ramzi Y. Dialkyl isocyanato tin alcoholate catalysts and dimers thereof
US5565603A (en) * 1993-12-20 1996-10-15 Saleh; Ramzi Y. Process for manufacturing dialkyl carbonate from urea and alcohol
WO1998000418A1 (en) * 1996-06-28 1998-01-08 Colgate-Palmolive Company Alkylene carbonates and their preparation
DE102004043990A1 (de) * 2004-09-11 2006-03-30 Lurgi Ag Verfahren zur Herstellung von Kohlensäureestern
US8877948B2 (en) 2008-10-08 2014-11-04 Arkema France Synthesis process of polyol carbonate from polyols, conducted in using a solvent selective for polyols carbonates
WO2014177558A1 (en) * 2013-04-29 2014-11-06 Total Research & Technology Feluy Process for preparing polycarbonates by polymerization of five-membered-ring cyclic carbonates
CN105358604A (zh) * 2013-04-29 2016-02-24 道达尔研究技术弗吕公司 通过五元环环状碳酸酯的聚合制备聚碳酸酯的工艺
CN105358604B (zh) * 2013-04-29 2017-09-26 道达尔研究技术弗吕公司 通过五元环环状碳酸酯的聚合制备聚碳酸酯的工艺
US20200024227A1 (en) * 2017-04-11 2020-01-23 Sabic Global Technologies B.V. Integrated process for production of glycerol carbonate (4-hydroxymethyl-2-oxo-1, 3-dioxolane) and urea
US11578034B2 (en) * 2017-04-11 2023-02-14 Sabic Global Technologies B.V. Integrated process for production of glycerol carbonate (4-hydroxymethyl-2-oxo-1, 3-dioxolane) and urea
CN111925351A (zh) * 2020-08-28 2020-11-13 华东理工大学 一种尿素与丙二醇（或乙二醇）连续溶解的方法

Also Published As

Publication number Publication date
JPH04211075A (ja) 1992-08-03
CA2032221A1 (en) 1991-08-21
EP0443758A1 (de) 1991-08-28
JP3085722B2 (ja) 2000-09-11

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